CN105229524A

CN105229524A - Aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal employing it represent element

Info

Publication number: CN105229524A
Application number: CN201480029320.8A
Authority: CN
Inventors: 佐藤夏树; 中原翔一朗; 石井秀则; 铃木加名子; 见山幸广
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2013-03-21
Filing date: 2014-03-20
Publication date: 2016-01-06
Also published as: KR20150134377A; TW201502202A; WO2014148596A1; JPWO2014148596A1

Abstract

The liquid crystal providing a kind of aligning agent for liquid crystal and liquid crystal orientation film and employ it represents element, described aligning agent for liquid crystal contains each polyamic acid comprising cellular construction shown in any one in following formula (I) and (II), this aligning agent for liquid crystal maintains after image and eliminates time and orientation constraining force and the transparency is also high, and be not easy, because of the un-symmetrical change of interchange driving, charge accumulation occurs, (in formula, R ¹represent the 4 valency organic groups forming fragrant family tetrabasic carboxylic acid, R ²represent the 4 valency organic groups forming tetrabasic carboxylic acid, R ³and R ⁴represent each the specific divalent organic group forming diamines.)。

Description

Aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal employing it represent element

Technical field

The present invention relates to and parallel electric field and the liquid crystal that drives are applied to substrate represent that aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal that employs it used in element represents element.

Background technology

All the time, liquid-crystal apparatus is widely used as the expressed portion of PC, mobile phone, TV imagescope etc.Liquid-crystal apparatus possesses: be such as clamped in the liquid crystal layer between device substrate and filter substrate, for liquid crystal layer is applied the pixel electrode of electric field and common electrode, for control the liquid crystal molecular orientation of liquid crystal layer alignment films, for switching the thin film transistor (TFT) (TFT) etc. of the electric signal to pixel electrode supply.As the type of drive of liquid crystal molecule, there will be a known the longitudinal electric field mode such as TN mode, VA mode; The Transverse electric-field types such as IPS mode, FFS mode.In general, with in the past to be formed at upper and lower base plate electrode application voltage and make liquid crystal drive longitudinal electric field mode compared with, only at the one-sided formation electrode of substrate and the Transverse electric-field type applying electric field along the direction being parallel to substrate as there is broad field angle characteristic and can representing that element is known by the liquid crystal that represents of high-quality.

Although the liquid crystal cells field angle excellent of Transverse electric-field type, the electrode part be formed in substrate is few, and when therefore the voltage retention of liquid crystal orientation film is weak, the voltage applied liquid crystal is insufficient, expression contrast reduces.In addition, electrostatic is likely to accumulate in liquid crystal cells, in addition, even if apply the asymmetric voltage produced because of driving, electric charge also can be accumulated in liquid crystal cells, these electric charges accumulated can be upset the orientation of liquid crystal or bring impact with the form of after image or ghost to representing, the expression quality of liquid crystal cell is significantly reduced.Especially, compared with longitudinal electric field mode, the pixel electrode in Transverse electric-field type and the distance of common electrode are near, and therefore highfield acts on alignment films, liquid crystal layer, thus there are these unfavorable conditions and easily become significant problem.

On the other hand, liquid crystal orientation film normally print aligning agent for liquid crystal and carry out drying, burn till after carry out brushing process and formed, Transverse electric-field type liquid crystal cells only has electrode structure at the one-sided of substrate, therefore substrate is greatly concavo-convex, in addition, the insulators such as silicon nitride are formed in substrate surface sometimes, seek the aligning agent for liquid crystal that printing is more excellent than existing alignment agent.And then, compared with liquid crystal cells in the past, exist easily because brushing process occurs to peel off or brushing consumption, these peel off or scar can reduce the problem representing quality.And then in IPS (In-PlaneSwitching) mode etc., to drive carried out in the mode of the liquid crystal molecule of horizontal alignment relative to substrate with transverse electric field, orientation constraining force also becomes important.If orientation constraining force is weak, then when driving liquid crystal for a long time, liquid crystal recovers less than original state, and contrast reduces or becomes the reason of ghost.

During for this transverse electric field driving liquid crystal cell, excellent and after image and the few aligning agent for liquid crystal of ghost as printing and resistance to brushing, patent documentation 1 discloses following aligning agent for liquid crystal, its by copolymerization or mixing containing being derived from the amic acid unit of aromatic tetracarboxylic acid and be derived from both amic acid unit of ester ring type tetrabasic carboxylic acid.In addition, as for obtaining liquid crystal aligning, orientation constraining force, brushing patience is excellent, voltage retention is high and the aligning agent for liquid crystal of the liquid crystal orientation film that charge accumulation is minimized, patent documentation 2 discloses following aligning agent for liquid crystal and represents element with the liquid crystal employing this aligning agent for liquid crystal, the feature of described aligning agent for liquid crystal is, it contains: specific insulation when making film is 1 × 10 ¹⁰~ 1 × 10 ¹⁴the low resistance polyimide precursor of Ω cm and there is high orientation polyimide precursor or the polyimide of ad hoc structure.

But, along with liquid crystal represents the high performance of element, the characteristic that liquid crystal orientation film requires also is become strict gradually, only utilizes during prior art and be difficult to satisfied whole requirement characteristic.

Prior art document

Patent documentation

Patent documentation 1: International Publication publication WO02/33481 pamphlet

Patent documentation 2: International Publication publication WO2004/53583 pamphlet

Summary of the invention

the problem that invention will solve

Along with Mobyneb mobile phone (smart mobile phone) in recent years, panel type terminal universal, the liquid crystal being equipped on them represents that element is when representing digital photograph, the contour image clearly of video, video recording, and requirement and TV, computer etc. are the expression performance of equal above high-quality.Such as, mobile phone, tablet terminal drive with battery substantially, therefore from this viewpoint of power saving, become stricter than ever for the raising of backlight utilization ratio, the i.e. requirement of the liquid crystal orientation film transparency.

In addition, the expression picture of mobile phone, tablet terminal or backlight switch, user continually just watch attentively from the moment starting to represent its in etc. there is the new problem different from exercise use.

Thus, the present inventor etc. as just start represent after characteristic correlation factor and be conceived to liquid crystal represent element interchange drive in asymmetry.That is, problem of the present invention is, obtains maintaining in the past necessary characteristic, especially after image and eliminates time and orientation constraining force, and the transparency is also high and be not easy the liquid crystal orientation film producing charge accumulation because exchanging the un-symmetrical change that drives.

for the scheme of dealing with problems

The present inventor etc. conduct in-depth research to solve above-mentioned problem, found that: in the high orientation polyimide precursor in liquid crystal orientation film disclosed in above-mentioned patent documentation 2, when using specific diamines as the divalent organic group with diamine structures, layer separating power improves, the liquid crystal orientation film showing excellent specific property can be obtained, thus complete the present invention.

That is, the invention provides a kind of aligning agent for liquid crystal, it contains: comprise at least a kind of polyamic acid of cellular construction shown in following formula (I) and comprise at least a kind of polyamic acid of cellular construction shown in following formula (II).

(R ¹represent the 4 valency organic groups be selected from following structure (III) and (IV) that can form fragrant family tetrabasic carboxylic acid,

R ²expression can form the 4 valency organic groups with following structure (V) or (V ') of tetrabasic carboxylic acid,

(R ⁵, R ⁶, R ⁷, R ⁸separately represent hydrogen atom or methyl)

R ³expression can form the divalent organic group with following structure (VI) or (VII) of diamines,

(R ¹²represent the alkylidene of carbon number 2 ~ 8)

R ⁴expression can form the divalent organic group be selected from following structure (VIII) or following structure (IX) of diamines,

(R ⁹, R ¹⁰separately be selected from hydrogen atom, methyl, ethyl, methoxyl, ethoxy, R ¹¹for ehter bond or methylene, a represents the integer of 1 ~ 4)

(R ¹³and R ¹⁴be the alkylidene of carbon number 1 ~ 3 independently of one another, Y ¹and Y ²be singly-bound ,-O-,-S-or ester bond independently of one another, Z is oxygen atom or sulphur atom).)

From another viewpoint of the present invention, provide liquid crystal orientation film to represent element with the liquid crystal employing it, described liquid crystal orientation film is coated on by above-mentioned aligning agent for liquid crystal on substrate and after burning till, carries out brushing process and formed.

the effect of invention

According to the present invention, can provide and maintain after image and eliminate time and orientation constraining force, and the transparency is also high and liquid crystal that is that be not easy to occur because exchanging the un-symmetrical change that drives the liquid crystal orientation film of charge accumulation, liquid crystal orientation film and employ it represents element.

Embodiment

Below describe the present invention in detail.

The feature of aligning agent for liquid crystal of the present invention is, it is the composition for the formation of liquid crystal orientation film, and it contains: have the polyamic acid 1 (being denoted as PAA1 below) of structural unit shown in general formula (I) and have the polyamic acid 2 (being denoted as PAA2 below) of structural unit shown in general formula (II).

About the content of PAA1 and PAA2, relative to both total amounts, PAA1 is 20 ~ 70 quality %, is more preferably 40 ~ 60 quality %, is most preferably 50 quality %.That is, relative to the total amount of PAA1 and PAA2, PAA2 is 80 ~ 30 quality %, is more preferably 60 ~ 40 quality %, is most preferably 50 quality %.When PAA1 is very few, orientation, the orientation constraining force of liquid crystal worsen, when PAA2 is very few, and the charge accumulation characteristic degradation of liquid crystal orientation film.PAA1 and PAA2 contained in aligning agent for liquid crystal of the present invention can be respectively a kind, also can be two or more.Can think in addition: in order to obtain the liquid crystal orientation film being not easy charge accumulation occurs because of the un-symmetrical change of interchange driving, preferably, when PAA1 and PAA2 mixing is made liquid crystal orientation film, the easy genetic horizon of these polyamic acids is separated.

Polyamic acid 1 (PAA1)

PAA1 is the polyimide precursor (polyamic acid) of high orientation component, has the structural unit shown in previously described formula (I).Comprise the liquid crystal aligning of the liquid crystal orientation film of these structures, orientation constraining force is excellent.The R of previously described formula (I) ¹comprise the 4 valency organic groups forming fragrant family tetrabasic carboxylic acid, they can be a kind, also can mix two or more and use.As the tetrabasic carboxylic acid with this structure, pyromellitic acid can be listed, 2, 3, 6, 7-naphthalene tetracarboxylic acid, 1, 2, 5, 6-naphthalene tetracarboxylic acid, 1, 4, 5, 8-naphthalene tetracarboxylic acid, 2, 3, 6, 7-anthracene tetrabasic carboxylic acid, 1, 2, 5, 6-anthracene tetrabasic carboxylic acid, 3, 3 ', 4, 4 '-biphenyltetracarboxyacid acid, 2, 3, 3 ', 4-biphenyltetracarboxyacid acid, two (3, 4-dicarboxyphenyi) ether, 3, 3 ', 4, 4 '-benzophenone tetrabasic carboxylic acid, two (3, 4-dicarboxyphenyi) sulfone, two (3, 4-dicarboxyphenyi) methane, 2, 2-two (3, 4-dicarboxyphenyi) propane, 1, 1, 1, 3, 3, 3-hexafluoro-2, 2 '-bis-(3, 4-dicarboxyphenyi) propane, two (3, 4-dicarboxyphenyi) dimethylsilane, two (3, 4-dicarboxyphenyi) diphenyl silane, 2, 3, 4, 5-pyridine tetrabasic carboxylic acid, 2, 6-two (3, 4-dicarboxyphenyi) pyridine etc., from the view point of reduction liquid crystal aligning and after image characteristic, R ¹preferably be selected from 4 valency organic groups in following structure,

As the tetrabasic carboxylic acid with this structure, pyromellitic acid, 2,3,6,7-naphthalene tetracarboxylic acids, 3 can be listed, 3 ', 4,4 '-biphenyltetracarboxyacid acid, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid, two (3,4-dicarboxyphenyi) ether etc., be especially more preferably pyromellitic acid.About these fragrant family tetrabasic carboxylic acids, at the R of the formula (I) of formation PAA1 ¹among, be more than at least 50 % by mole, be preferably more than 70 % by mole, more than 80 % by mole or more than 90 % by mole.

In addition, in previously described formula (I), R ³comprise and form the divalent organic group of diamines together with-NH-part, can be a kind, also can mix and there is two or more, any one or both the divalent organic group at least a kind of needs contained (VI) or formula (VII).

The R of above-mentioned formula (VII) ¹²be preferably the alkylidene of carbon number 2 ~ 8, be more preferably the alkylidene of carbon number 3 ~ 6, include, for example out propylidene, butylidene, pentylidene and hexylidene etc., more preferably the butylidene of carbon number 4 or 5 or pentylidene.

In a preferred embodiment of the present invention, the R in formula (I) ³for forming the divalent organic group of two (4-amino-benzene oxygen) benzene of 1,3-or two (4-amino-benzene oxygen) pentane of 1,5-.

The R of formula (I) ³in the R with these ad hoc structures ³ratio be preferably 10 ~ 100 % by mole, be more preferably 50 ~ 100 % by mole.When this ratio is very few, the variation characteristic of flicker worsens sometimes.With the R with above-mentioned ad hoc structure ³other R that mixing exists ³structure be not particularly limited.

Below list and form R ³the concrete example of other diamine compound of structure.P-phenylenediamine (PPD) can be listed, 2,3,5,6-tetramethyl-para-phenylene diamine, 2,5-dimethyl-p-phenylenediamine, m-phenylene diamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diamido benzylalcohol, 2,4-diamido benzylalcohol, 4,6-diaminoresorcinol, 4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dihydroxy-4,4 '-benzidine, 3,3 '-two fluoro-4,4 '-benzidine, 3,3 '-trifluoromethyl-4,4 '-benzidine, 3,4 '-benzidine, 3,3 '-benzidine, 2,2 '-benzidine, 2,3 '-benzidine, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 2,2 '-diaminodiphenyl-methane, 2,3 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl ether, 3,3 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 2,2 '-diaminodiphenyl ether, 2,3 '-diaminodiphenyl ether, diaphenylsulfone, 3,3 '-sulfonyldianiline, two (4-aminophenyl) silane, two (3-aminophenyl) silane, dimethyl-bis-(4-aminophenyl) silane, dimethyl-bis-(3-aminophenyl) silane, 4,4 '-phenothiazine, 3,3 '-phenothiazine, 4,4 '-diamino-diphenyl amine, 3,3 '-diamino-diphenyl amine, 3,4 '-diamino-diphenyl amine, 2,2 '-diamino-diphenyl amine, 2,3 '-diamino-diphenyl amine, N-methyl (4,4 '-diamino-diphenyl) amine, N-methyl (3,3 '-diamino-diphenyl) amine, N-methyl (3,4 '-diamino-diphenyl) amine, N-methyl (2,2 '-diamino-diphenyl) amine, N-methyl (2,3 '-diamino-diphenyl) amine, 4,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, Isosorbide-5-Nitrae-diaminonaphthalene, 2,2 '-diaminobenzophenone, 2,3 '-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, two (4-aminophenyl) ethane of 1,2-, two (3-aminophenyl) ethane of 1,2-, two (4-aminophenyl) propane of 1,3-, two (3-aminophenyl) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminophenyl) butane, Isosorbide-5-Nitrae-bis-(3-aminophenyl) butane, two (3,5-diethyl-4-aminophenyl) methane, Isosorbide-5-Nitrae-bis-(4-aminophenyl) benzene, two (4-aminophenyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminobenzyl) benzene, two (4-aminophenethyl) urea of 1,3-, N-methyl-2-(4-aminophenyl) ethamine, 4,4 '-[Isosorbide-5-Nitrae-phenylene two (methylene)] diphenylamine, 4,4 '-[1,3-phenylene two (methylene)] diphenylamine, 3,4 '-[Isosorbide-5-Nitrae-phenylene two (methylene)] diphenylamine, 3,4 '-[1,3-phenylene two (methylene)] diphenylamine, 3,3 '-[Isosorbide-5-Nitrae-phenylene two (methylene)] diphenylamine, 3,3 '-[1,3-phenylene two (methylene)] diphenylamine, Isosorbide-5-Nitrae-phenylene two [(4-aminophenyl) ketone], Isosorbide-5-Nitrae-phenylene two [(3-aminophenyl) ketone], 1,3-phenylene two [(4-aminophenyl) ketone], 1,3-phenylene two [(3-aminophenyl) ketone], Isosorbide-5-Nitrae-phenylene two (PABA ester), Isosorbide-5-Nitrae-phenylene two (3-Aminobenzoate), 1,3-phenylene two (PABA ester), 1,3-phenylene two (3-Aminobenzoate), two (4-aminophenyl) terephthalate, two (3-aminophenyl) terephthalate, two (4-aminophenyl) isophthalic acid ester, two (3-aminophenyl) isophthalic acid ester, N, N '-(Isosorbide-5-Nitrae-phenylene) two (4-aminobenzamide), N, N '-(1,3-phenylene) two (4-aminobenzamide), N, N '-(Isosorbide-5-Nitrae-phenylene) two (3-AB), N, N '-(1,3-phenylene) two (3-AB), N, N '-bis-(4-aminophenyl) terephthalamide, N, N '-bis-(3-aminophenyl) terephthalamide, N, N '-bis-(4-aminophenyl) isophtalamide, N, N '-bis-(3-aminophenyl) isophtalamide, two (4-aminophenyl) anthracene of 9,10-, 4,4 '-bis-(4-amino-benzene oxygen) diphenyl sulfone, 2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2 '-bis-(4-aminophenyl) HFC-236fa, 2,2 '-bis-(3-aminophenyl) HFC-236fa, 2,2 '-bis-(3-amino-4-aminomethyl phenyl) HFC-236fa, 2,2 '-bis-(4-aminophenyl) propane, 2,2 '-bis-(3-aminophenyl) propane, 2,2 '-bis-(3-amino-4-aminomethyl phenyl) propane, two (3-amino-benzene oxygen) propane of 1,3-, Isosorbide-5-Nitrae-bis-(3-amino-benzene oxygen) butane, two (3-amino-benzene oxygen) pentane of 1,5-, two (3-amino-benzene oxygen) hexane of 1,6-, 1,7-(3-amino-benzene oxygen) heptane, two (3-amino-benzene oxygen) octane of 1,8-, two (4-amino-benzene oxygen) nonane of 1,9-, two (3-amino-benzene oxygen) nonane of 1,9-, 1,10-(4-amino-benzene oxygen) decane, 1,10-(3-amino-benzene oxygen) decane, 1,11-(4-amino-benzene oxygen) undecane, 1,11-(3-amino-benzene oxygen) undecane, 1,12-(4-amino-benzene oxygen) dodecane, 1,12-(3-amino-benzene oxygen) dodecane, two (4-aminocyclohexyl) methane, two (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropanes, 1,4-Diaminobutane, 1,5-1,5-DAP, 1,6-diamino hexane, 1,7-diaminoheptane, 1,8-diamino-octane, 1,9-diamino nonane, 1,10-diamino decane, 1,11-diamino undecane, 1,12-diamino dodecane etc.Wherein, from the view point of good orientation etc., preferably use 4,4 '-diaminodiphenyl-methane, 1,3-two (4-aminophenethyl) urea, N-methyl-2-(4-aminophenyl) ethamine.

Other diamine compound more than enumerated may be used singly or in combination of two or more according to characteristics such as specific insulation, brushing patience, ion concentration characteristic, transmissivity, liquid crystal aligning, voltage retention performance and accumulated charge when making liquid crystal orientation film.

In formula (VI), one or more hydrogen atoms any on phenyl ring are optionally replaced by 1 valency organic group beyond primary amino radical.As this 1 valency organic group, the alkyl of carbon number 1 ~ 20, the thiazolinyl of carbon number 2 ~ 20, the alkoxy of carbon number 1 ~ 20, the fluorine-containing thiazolinyl containing fluoroalkyl, carbon number 2 ~ 20 of carbon number 1 ~ 20, the fluoroalkoxy of carbon number 1 ~ 20, cyclohexyl, phenyl, fluorine atom can be listed or comprise their group etc. of combination.From the view point of liquid crystal aligning, be preferably selected from by 1 valency organic group in the group formed containing fluoroalkyl, the fluorine-containing thiazolinyl of carbon number 2 ~ 4 and the fluoroalkoxy of carbon number 1 ~ 4 of the alkoxy of the thiazolinyl of the alkyl of carbon number 1 ~ 4, carbon number 2 ~ 4, carbon number 1 ~ 4, carbon number 1 ~ 4.Preferred structure is that the hydrogen atom on phenyl ring is not substituted.

As the diamines of structure with above-mentioned formula (VI), can 1 be listed, two (4-amino-benzene oxygen) benzene, 1 of 3-, two (4-amino-benzene oxygen) benzene of 4-etc., from the variation characteristic this point of flicker, be preferably two (4-amino-benzene oxygen) benzene of 1,3-.

Polyamic acid 2 (PAA2)

PAA2 is the polyimide precursor (polyamic acid) of the composition of the charge accumulation characteristic contributing to liquid crystal orientation film, has the structural unit shown in general formula (II).When this polyamic acid being made film, shown specific insulation is preferably 1 × 10 ¹⁰~ 1 × 10 ¹⁴Ω cm.When this resistivity is too high, the expression ghost/inequality of occurring source self charge accumulation sometimes, when this resistivity is too low, voltage retention performance is deteriorated sometimes.

The R of general formula (II) ²comprise the 4 valency organic groups forming tetrabasic carboxylic acid, they can be a kind, also can mix two or more and use.As the tetrabasic carboxylic acid with this structure, 1,2,3,4-cyclo-butane tetrabasic carboxylic acid, 1 can be listed, 2,3,4-cycloheptane tetrabasic carboxylic acid, 2,3,4,5-tetrahydrofuran tetrabasic carboxylic acid, 1,2,4,5-cyclopentanetetracarboxylic, 3,4-dicarboxyl-1-cyclohexyl succinic acids, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic, dicyclo [3,3,0] octane-2,4,6,8-tetrabasic carboxylic acid, 2,3,5-tricarboxylic cyclopentyl acetic acid etc., from the view point of the electrical characteristics of gained element, R ²preferably be selected from 4 valency organic groups in following structure (V) and (V '),

(R ⁵, R ⁶, R ⁷, R ⁸separately represent hydrogen atom or methyl)

As the tetrabasic carboxylic acid with this structure, 1,2,3,4-cyclo-butane tetrabasic carboxylic acid or 1,2,3,4-butane tetracarboxylic acid dianhydride or their derivant etc. can be listed, especially, be more preferably 1,2,3,4-cyclo-butane tetrabasic carboxylic acid.About these tetrabasic carboxylic acids, at the R of the formula (II) of formation PAA2 ²among, be at least more than 50 % by mole, be preferably more than 70 % by mole, more than 80 % by mole or more than 90 % by mole.Other R ²structure be not particularly limited, can 1 be used, 2,3,4-cycloheptane tetrabasic carboxylic acid, 2,3,4,5-tetrahydrofuran tetrabasic carboxylic acids, 1,2,4,5-cyclopentanetetracarboxylic, 3,4-dicarboxyl-1-cyclohexyl succinic acids, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic, dicyclo [3,3,0] octane-2,4,6,8-tetrabasic carboxylic acid, 2,3,5-tricarboxylic cyclopentyl acetic acid etc.

The R of previously described formula (II) ⁴for forming the divalent organic group of diamines, they can be the same or different each other, can be a kind in addition and also can mix two or more use.As the diamines with these structures, p-phenylenediamine (PPD), m-phenylene diamine, 2 can be listed, 5-diaminotoluene, 2,6-diaminotoluene, 4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-benzidine, diaminodiphenyl-methane, diaminodiphenyl ether, 2, the aromatic diamines such as 2 '-diamino-diphenyl propane, two (3,5-diethyl-4-aminophenyl) methane, 1,3-two (4-aminophenethyl) ureas.Among these, from the view point of after image characteristic, R ⁴preferably separately be selected from the divalent organic group in following structure (VIII) and (IX).

(R ¹³and R ¹⁴be the alkylidene of carbon number 1 ~ 3 independently of one another, Y ¹and Y ²be singly-bound ,-O-,-S-or ester bond independently of one another, Z is oxygen atom or sulphur atom.)

As the diamines with this structure, can 4 be listed, 4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 2,2 '-diaminodiphenyl-methane, 2,3 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl ether, 3,3 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 2,2 '-diaminodiphenyl ether, 2,3 '-diaminodiphenyl ether, 1,3-two (4-aminophenethyl) ureas etc.There is the R of these ad hoc structures ⁴ratio be preferably 50 ~ 100 % by mole, when this ratio is very few, after image characteristic worsens sometimes.

In addition, within the scope without prejudice to the object of the present invention, can with the R with above-mentioned ad hoc structure ⁴mixing exists and uses other diamines, and they can be a kind, also can mix two or more and use.As its concrete example, p-phenylenediamine (PPD) can be listed, 2,3,5,6-tetramethyl-para-phenylene diamine, 2,5-dimethyl-p-phenylenediamine, m-phenylene diamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diamido benzylalcohol, 2,4-diamido benzylalcohol, 4,6-diaminoresorcinol, 4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dihydroxy-4,4 '-benzidine, 3,3 '-two fluoro-4,4 '-biphenyl, 3,3 '-trifluoromethyl-4,4 '-benzidine, 3,4 '-benzidine, 3,3 '-benzidine, 2,2 '-benzidine, 2,3 '-benzidine, diaphenylsulfone, 3,3 '-sulfonyldianiline, two (4-aminophenyl) silane, two (3-aminophenyl) silane, dimethyl-bis-(4-aminophenyl) silane, dimethyl-bis-(3-aminophenyl) silane, 4,4 '-phenothiazine, 3,3 '-phenothiazine, 4,4 '-diamino-diphenyl amine, 3,3 '-diamino-diphenyl amine, 3,4 '-diamino-diphenyl amine, 2,2 '-diamino-diphenyl amine, 2,3 '-diamino-diphenyl amine, N-methyl (4,4 '-diamino-diphenyl) amine, N-methyl (3,3 '-diamino-diphenyl) amine, N-methyl (3,4 '-diamino-diphenyl) amine, N-methyl (2,2 '-diamino-diphenyl) amine, N-methyl (2,3 '-diamino-diphenyl) amine, 4,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, Isosorbide-5-Nitrae-diaminonaphthalene, 2,2 '-diaminobenzophenone, 2,3 '-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, two (4-aminophenyl) ethane of 1,2-, two (3-aminophenyl) ethane of 1,2-, two (4-aminophenyl) propane of 1,3-, two (3-aminophenyl) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminophenyl) butane, Isosorbide-5-Nitrae-bis-(3-aminophenyl) butane, two (3,5-diethyl-4-aminophenyl) methane, Isosorbide-5-Nitrae-bis-(4-aminophenyl) benzene, two (4-aminophenyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminobenzyl) benzene, two (4-aminophenethyl) urea of 1,3-, N-methyl-2-(4-aminophenyl) ethamine, 4,4 '-[Isosorbide-5-Nitrae-phenylene two (methylene)] diphenylamine, 4,4 '-[1,3-phenylene two (methylene)] diphenylamine, 3,4 '-[Isosorbide-5-Nitrae-phenylene two (methylene)] diphenylamine, 3,4 '-[1,3-phenylene two (methylene)] diphenylamine, 3,3 '-[Isosorbide-5-Nitrae-phenylene two (methylene)] diphenylamine, 3,3 '-[1,3-phenylene two (methylene)] diphenylamine, Isosorbide-5-Nitrae-phenylene two [(4-aminophenyl) ketone], Isosorbide-5-Nitrae-phenylene two [(3-aminophenyl) ketone], 1,3-phenylene two [(4-aminophenyl) ketone], 1,3-phenylene two [(3-aminophenyl) ketone], Isosorbide-5-Nitrae-phenylene two (PABA ester), Isosorbide-5-Nitrae-phenylene two (3-Aminobenzoate), 1,3-phenylene two (PABA ester), 1,3-phenylene two (3-Aminobenzoate), two (4-aminophenyl) terephthalate, two (3-aminophenyl) terephthalate, two (4-aminophenyl) isophthalic acid ester, two (3-aminophenyl) isophthalic acid ester, N, N '-(Isosorbide-5-Nitrae-phenylene) two (4-aminobenzamide), N, N '-(1,3-phenylene) two (4-aminobenzamide), N, N '-(Isosorbide-5-Nitrae-phenylene) two (3-AB), N, N '-(1,3-phenylene) two (3-AB), N, N '-bis-(4-aminophenyl) terephthalamide, N, N '-bis-(3-aminophenyl) terephthalamide, N, N '-bis-(4-aminophenyl) isophtalamide, N, N '-bis-(3-aminophenyl) isophtalamide, two (4-aminophenyl) anthracene of 9,10-, 4,4 '-bis-(4-amino-benzene oxygen) diphenyl sulfone, 2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2 '-bis-(4-aminophenyl) HFC-236fa, 2,2 '-bis-(3-aminophenyl) HFC-236fa, 2,2 '-bis-(3-amino-4-aminomethyl phenyl) HFC-236fa, 2,2 '-bis-(4-aminophenyl) propane, 2,2 '-bis-(3-aminophenyl) propane, 2,2 '-bis-(3-amino-4-aminomethyl phenyl) propane, two (4-amino-benzene oxygen) propane of 1,3-, two (3-amino-benzene oxygen) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) butane, Isosorbide-5-Nitrae-bis-(3-amino-benzene oxygen) butane, two (4-amino-benzene oxygen) pentane of 1,5-, two (3-amino-benzene oxygen) pentane of 1,5-, two (4-amino-benzene oxygen) hexane of 1,6-, two (3-amino-benzene oxygen) hexane of 1,6-, two (4-amino-benzene oxygen) heptane of 1,7-, 1,7-(3-amino-benzene oxygen) heptane, two (4-amino-benzene oxygen) octane of 1,8-, two (3-amino-benzene oxygen) octane of 1,8-, two (4-amino-benzene oxygen) nonane of 1,9-, two (3-amino-benzene oxygen) nonane of 1,9-, 1,10-(4-amino-benzene oxygen) decane, 1,10-(3-amino-benzene oxygen) decane, 1,11-(4-amino-benzene oxygen) undecane, 1,11-(3-amino-benzene oxygen) undecane, 1,12-(4-amino-benzene oxygen) dodecane, 1,12-(3-amino-benzene oxygen) dodecane.Two (4-aminocyclohexyl) methane, two (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropanes, 1,4-diaminobutane, 1,5-1,5-DAP, 1,6-diamino hexane, 1,7-diaminoheptane, 1,8-diamino-octane, 1,9-diamino nonane, 1,10-diamino decane, 1,11-diamino undecane, 1,12-diamino dodecane etc.Wherein, from viewpoints such as good electrical characteristics, preferably use 1,3-two (4-aminophenethyl) urea.

The synthesis of polyamic acid

By the reaction of tetracarboxylic dianhydride and diamines and when obtaining the polyamic acid for PAA1 or PAA2, tetracarboxylic dianhydride and diamines are mixed in organic solvent and the method making it react is easy.

As long as the solvent that the polyamic acid that the organic solvent used during above-mentioned reaction generates can dissolve just is not particularly limited.When enumerating its concrete example obstinately, N can be listed, dinethylformamide, DMA, METHYLPYRROLIDONE, N-methyl caprolactam, dimethyl sulfoxide (DMSO), tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton etc.They can be used alone, also can be used in combination.And then, even the solvent of insoluble solution polyamic acid, in the scope that generated polyamic acid can not be separated out, also can be mixed in above-mentioned solvent and use.In addition, the moisture in organic solvent can hinder polyreaction and then become the reason making generated polyamic acid that hydrolysis occur, and therefore organic solvent preferably dehydrates rear use as far as possible.

As the method making tetracarboxylic dianhydride's composition and diamine component mix in organic solvent, following method can be listed: stir and make diamine component be dispersed or dissolved in the solution of organic solvent, the method for directly adding tetracarboxylic dianhydride's composition or making tetracarboxylic dianhydride's composition be dispersed or dissolved in organic solvent to add; Otherwise, be dispersed or dissolved in the method for adding diamine component in the solution of organic solvent to making tetracarboxylic dianhydride's composition; Alternately adding the method etc. of tetracarboxylic dianhydride's composition and diamine component, in the present invention, can be the either method among these.In addition, when tetracarboxylic dianhydride's composition or diamine component comprise multiple compounds, these Multiple components can react under the state be pre-mixed, and also can react successively respectively.

Temperature when tetracarboxylic dianhydride's composition and diamine component are reacted in organic solvent is generally 0 ~ 150 DEG C, is preferably 5 ~ 100 DEG C, is more preferably 10 ~ 80 DEG C.During temperature height, polyreaction can terminate fast, but when temperature is too high, sometimes can not get the polymkeric substance of high molecular.In addition, reaction can be carried out with any concentration, when concentration is too low, is difficult to the polymkeric substance obtaining high molecular, and during excessive concentration, the viscosity of reactant liquor becomes too high, is difficult to uniform stirring, is therefore preferably 1 ~ 50 quality %, is more preferably 5 ~ 30 quality %.Initial reaction stage can be carried out with high concentration, and is adding organic solvent thereafter.

The tetracarboxylic dianhydride's composition used in the polyreaction of polyamic acid: the ratio of diamine component is preferably 1:0.8 ~ 1.2 with molar ratio computing.In addition, make diamine component excessive and the polyamic acid that obtains sometimes the painted of solution become obvious, therefore when noticing that solution is painted, above-mentioned ratio is set to 1:0.8 ~ 1.In the same manner as common polycondensation reaction, this mol ratio is more close to 1:1, then the molecular weight of gained polyamic acid becomes larger.When the molecular weight of polyamic acid is too small, the coating strength obtained thus is sometimes insufficient, otherwise, when the molecular weight of polyamic acid is excessive, solution viscosity when sometimes aligning agent for liquid crystal being made coating solution becomes too high, forms workability, painting film uniformity variation during film.

In addition, the weight-average molecular weight of this polyamic acid is preferably 5, and 000 ~ 300,000, be more preferably 10,000 ~ 200,000, as number-average molecular weight, be preferably 2,500 ~ 150,000, be more preferably 5,000 ~ 100,000.

When not wish in aligning agent for liquid crystal of the present invention containing solvent for the polymerization of polyamic acid, exist in reaction solution unreacted monomer component, impurity and want to be removed time, the precipitation of carrying out polyamic acid reclaims and refines.About its method, easy, polyamic acid solution is fed into the poor solvent in stirring, and carries out precipitating the method reclaimed.As the poor solvent used in the precipitation recovery of polyamic acid, be not particularly limited, methyl alcohol, acetone, hexane, butyl cellosolve, heptane, MEK, methyl isobutyl ketone, ethanol, toluene, benzene etc. can be exemplified.The polyamic acid precipitated by being fed into poor solvent filter/is cleaning and after reclaiming, is carrying out air drying or heat drying under normal or reduced pressure, thus can make powder.Repeatedly carry out 2 ~ 10 times this powder is dissolved in good solvent further and reppd operation time, can also polyamic acid be refined.When utilizing primary sedimentation reclaimer operation cannot eliminate impurity, preferably carry out this refining step.As poor solvent now, when using the poor solvent of such as alcohols, ketone, hydrocarbon etc. more than 3 kinds, purification efficiency rises further, so preferably.Even if above-mentioned precipitation reclaims and purification operations also can be carried out equally when the synthesis of aftermentioned polyamic acid Arrcostab, polyimide.

When polyamic acid partially or completely being carried out imidizate, its manufacture method is not particularly limited, and directly can carry out imidizate in the solution by making the polyamic acid of tetracarboxylic dianhydride and diamine reactant.Now, in order to make part or all polyamic acid change into polyimide, can adopt and make the method for its dehydration closed-loop by heating, using known dehydration closed-loop catalyzer to carry out the method for chemical closed loop.In the method based on heating, the 100 DEG C ~ arbitrary temp of 300 DEG C, preferably 120 DEG C ~ 250 DEG C can be selected.In the method for chemical closed loop, such as, can use pyridine, triethylamine etc. under the existence of acetic anhydride etc., temperature now can select the arbitrary temp of-20 DEG C ~ 200 DEG C.

Aligning agent for liquid crystal

The form of the aligning agent for liquid crystal of the present invention below illustrated is the coating fluid containing PAA1 and PAA2, as long as but uniform film can be formed on substrate, then also can be other form.In order to make the coating fluid containing PAA1 and PAA2, the reaction solution of each polyamic acid directly can be mixed, also can mix after making the polyamic acid of solid matter be dissolved in organic solvent, in addition, can also mix while making the polyamic acid of solid matter be dissolved in organic solvent.The mixture ratio of PAA1 and PAA2 is preferably 2:8 ~ 7:3 in mass ratio (PAA1:PAA2), is more preferably 3:8 ~ 7:3, more preferably 4:6 ~ 6:4, is particularly preferably about 5:5 as described above.By making these ratios within the scope of this, liquid crystal aligning and all good aligning agent for liquid crystal of electrical characteristics can be obtained.

As this organic solvent, as long as the solvent of the resinous principle contained by dissolving, just be not particularly limited, when enumerating its concrete example obstinately, N can be listed, dinethylformamide, N, N-dimethyl acetamide, METHYLPYRROLIDONE, N-methyl caprolactam, 2-Pyrrolidone, N-ethyl pyrrolidone, NVP, dimethyl sulfoxide (DMSO), tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton etc., they can use a kind also can mix multiple use.

In addition, when being used alone, even do not dissolve the solvent of resinous principle, as long as in the scope that resinous principle can not be separated out, then also can be mixed in aligning agent for liquid crystal of the present invention.Especially it is known that, ethyl cellosolve is had by suitably mixing, butyl cellosolve, ethyl carbitol, butyl carbitol, ethylcarbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic acid esters, propylene glycol-1-single ether-2-acetic acid esters, dipropylene glycol, 2-(2-ethoxy propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactates etc. have the solvent of low surface tension, painting film uniformity when being applied to substrate improves, also can compatibly for aligning agent for liquid crystal of the present invention.

Coating fluid as aligning agent for liquid crystal of the present invention suitably can change the concentration of solid constituent according to the thickness setting of the liquid crystal orientation film that will be formed, be preferably set to 1 ~ 10 quality %.During less than 1 quality %, be difficult to form even and flawless film, during more than 10 quality %, the storage stability of solution is deteriorated sometimes.

In addition, in order to improve the adaptation of film and substrate, aligning agent for liquid crystal of the present invention can add the adjuvants such as silane coupling agent, in addition, also can add other resinous principle.

As above to operate and after the aligning agent for liquid crystal of the present invention that obtains filters as required, coat substrate and dry, burn till, thus film can being made, by carrying out brushing to this coated surface, illumination is penetrated etc. orientation process, can liquid crystal orientation film be used as.

Now, as substrate used, as long as the high substrate of the transparency is just not particularly limited, the plastic bases etc. such as glass substrate, acrylic compounds substrate, polycarbonate substrate can be used, from the view point of Simplified flowsheet, preferably use the substrate of the ITO electrode be formed with for driving liquid crystal etc.In addition, the liquid crystal of reflection-type represents in element, if be only one-sided substrate, can use the opaque materials such as silicon wafer, and electrode now also can use the material of the meeting reflected light such as aluminium.

As the coating process of aligning agent for liquid crystal, can list spin-coating method, print process, ink-jet method etc., from the aspect of throughput rate, the industrial hectographic printing method that widely uses, is also applicable to aligning agent for liquid crystal of the present invention.

Drying process after coating of liquid crystalline alignment agent is not necessarily necessary, for after coating ~ burn till till time each substrate disunity time or coating after do not burn till immediately time, preferably include drying process.As long as solvent is evaporated to the degree that film shape can not be out of shape because of transport of substrate etc. by this drying, be not particularly limited for these dry means.If list concrete example, then can to adopt on the hot plate of 50 ~ 150 DEG C, preferably 80 ~ 120 DEG C dry 0.5 ~ 30 minute, the preferred method of dry 1 ~ 5 minute.

Burning till of aligning agent for liquid crystal can be carried out with the arbitrary temp of 100 ~ 350 DEG C, is preferably 150 DEG C ~ 300 DEG C, more preferably 200 DEG C ~ 250 DEG C.Time in aligning agent for liquid crystal containing polyimide precursor, the conversion ratio being changed into polyimide by polyimide precursor changes because of this firing temperature, but aligning agent for liquid crystal of the present invention not necessarily needs 100% to carry out imidizate.Wherein, preferably, burn till with the temperature of high more than 10 DEG C of the heat treatment temperature than sealant cures necessary in liquid crystal cells manufacturing process etc.

When coating thickness after burning till is blocked up, be disadvantageous in the power consumption representing element at liquid crystal, when the coating thickness after burning till is crossed thin, liquid crystal represents that the reliability of element reduces sometimes, is therefore 5 ~ 300nm, is preferably 10 ~ 100nm.

Liquid crystal represents element

Liquid crystal of the present invention represents that element obtains as follows: after utilizing said method to be obtained being with the substrate of liquid crystal orientation film by aligning agent for liquid crystal of the present invention, utilize known method to make liquid crystal cells, thus make liquid crystal and represent element.An example of liquid crystal cells is made if list, usual way is, be generally 1 ~ 30 μm with clamping, be preferably the sept of 2 ~ 10 μm and the mode at any angle that brushing direction is preferably 0 ~ 270 ° arranges the 1 pair of substrate being formed with liquid crystal orientation film, surrounding sealant is fixed, and injects liquid crystal and seals.Existing brushing device can be used to the brushing process that liquid crystal orientation film carries out.As the material of brushing cloth now, cotton, rayon, nylon etc. can be listed.Inclosure method about liquid crystal is not particularly limited, and can exemplify: make, in made liquid crystal cells after decompression, to inject the vacuum method of liquid crystal; Drip the dripping method etc. of the laggard row sealing of liquid crystal.

Such operation, the liquid crystal using aligning agent for liquid crystal of the present invention to make represents that the liquid crystal aligning of element, orientation constraining force are excellent, and has excellent electrical characteristics, therefore, it is possible to make the liquid crystal display device that contrast is not easy to reduce, be less likely to occur ghost.These liquid crystal represent among element, and the lateral electric-field type liquid crystal being particularly preferred for easily occurring because of orientation constraining force ghost represents element.

Embodiment

Below, for the detail of manufacture method of the present invention, list and the embodiment etc. of raw material composition, the experimental technique studied of compounding ratio and result thereof and typical manufacture method is described.It should be noted that, the present invention is not limited to these embodiments.

The explanation of the abbreviation used in the present embodiment

(tetracarboxylic dianhydride)

CA-1: pyromellitic dianhydride

CA-2:1,2,3,4-cyclo-butane tetracarboxylic dianhydride

CA-3:3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride

(diamines)

DA-1:4,4 '-diaminodiphenyl ether

DA-2:4,4 '-diaminodiphenyl-methane

Two (4-aminophenethyl) urea of DA-3:1,3-

Two (4-amino-benzene oxygen) benzene of DA-4:1,3-

Two (4-amino-benzene oxygen) pentane of DA-5:1,5-

DA-6:4,4 '-diamino-diphenyl amine

DA-7:N-methyl-2-(4-aminophenyl) ethamine

Two (4-amino-benzene oxygen) propane of DA-8:1,3-

(organic solvent)

NMP:N-N-methyl-2-2-pyrrolidone N-

GBL: gamma-butyrolacton

BCS: butyl cellosolve

Each assay method is below shown.

(transmissivity measures (evaluation of visual perspective rate))

After the metre filter gained aligning agent for liquid crystal of 1.0 μm, spin coating alignment agent on a quartz substrate, on the hot plate of 50 DEG C after dry 5 minutes, burns till 30 minutes with 230 DEG C, thus formation thickness is the polyimide film of 100nm.Only at the both sides sticking two-faced adhesive tape of the coated surface towards this substrate, fit with the quartz base plate of completely non-film forming.Injection liquid paraffin body in the simple and easy unit made like this, the UV-3100PC using Shimadzu Seisakusho Ltd. to manufacture measures transmissivity.Calculate visual perspective rate by the data obtained, define and be evaluated as " bad " when defining when this value is more than 96% and be evaluated as " well ", this value less than 96%.Evaluation result is shown in table 3.

First electroded substrate is prepared.Substrate is of a size of 30mm × 50mm and thickness is the glass substrate of 0.7mm.On substrate, as the 1st layer, define for forming counter electrode and possessing the ITO electrode of solid shape pattern.On the counter electrode of the 1st layer, as the 2nd layer, define SiN (silicon nitride) film utilizing CVD and film forming.The thickness of the 2nd layer of SiN film is 500nm, and it plays function as interlayer dielectric.On the SiN film of the 2nd layer, as the 3rd layer, configure the comb teeth-shaped pixel electrode formed by ito film patterning, thus form the 1st pixel and these two pixels of the 2nd pixel.The size of each pixel is: long 10mm and be widely about 5mm.Now, the counter electrode of the 1st layer and the pixel electrode of the 3rd layer are electrical isolation because of the effect of the SiN film of the 2nd layer.

The pixel electrode of the 3rd layer has the comb teeth-shaped shape that " く " font electrode key element that middle body bends is formed through multiple arrangement.The width of the Width of each electrode key element is 3 μm, is spaced apart 6 μm between electrode key element." く " font multiple arrangement of electrode key element that the pixel electrode forming each pixel is bent by middle body and forming, therefore the shape of each pixel is not oblong-shaped, and possess in the same manner as electrode key element middle body bend, the shape of " く " word of being similar to runic.Further, each pixel for boundary is split up and down, has the 2nd region of the 1st region on the upside of sweep and downside with the sweep of these central authorities.

When contrasting the 1st region and the 2nd region of each pixel, the formation direction forming the electrode key element of their pixel electrode is different.Namely, during using the brushing direction of aftermentioned liquid crystal orientation film as benchmark, in the 1st region of pixel, the electrode key element of pixel electrode is formed in the mode of the angle (clockwise) presenting+10 °, in the 2nd region of pixel, form the electrode key element of pixel electrode in the mode of the angle (clockwise) presenting-10 °.That is, the 1st region of each pixel and the 2nd region are formed as follows: the liquid crystal brought out by applying voltage between pixel electrode and counter electrode, the direction reverse direction each other of spinning movement (plane switches) in real estate.

Then, after the metre filter gained aligning agent for liquid crystal of 1.0 μm, be spun on prepared above-mentioned electroded substrate and the glass substrate as subtend substrate respectively, film forming has ito film and has described glass substrate is overleaf highly the column spacer of 4 μm.Then, on the hot plate of 50 DEG C after dry 5 minutes, burning till 30 minutes at 230 DEG C, is that the form of the film of 70nm obtains polyimide film on each substrate with thickness.After this polyimide film carries out brushing (roller footpath is 120mm, rotating speed is 500rpm, translational speed is 30mm/ second, amount of compression be 0.3mm) along specific brushing direction rayon cloth, the ultrasonic irradiation of 1 minute is carried out, with 80 DEG C of dryings 10 minutes in pure water.

Thereafter, using 2 kinds of substrates of above-mentioned band liquid crystal orientation film, is that antiparallel mode combines with respective brushing direction, and seal with leaving liquid crystal injecting port around, production unit gap is the dummy cell of 3.6 μm.After injecting liquid crystal (MLC-2041, MERCKCORPORATION system) to vacuum in this dummy cell at normal temperatures, sealing inlet and make the liquid crystal cells of antiparallel orientations.The liquid crystal that gained liquid crystal cells forms IPS pattern represents element.Thereafter, by gained liquid crystal cells with 110 DEG C of heating 1 hour, place after a Dinner for each evaluation.

(after image evaluation)

Following optics system etc. is used to carry out the evaluation of after image.

Be arranged on by made liquid crystal cells between 2 polarization plates configuring in the mode that polarization axle is vertical, light LED-backlit not executing under alive state, the arrangement angles of adjustment liquid crystal cells, reaches minimum to make the brightness of transmitted light.

Then, applying frequency to this liquid crystal cells is the alternating voltage of 30Hz, while measure V-T curve (voltage-transmission rate curve), alternating voltage relative transmittance being reached 23% calculates as driving voltage.

During after image is evaluated, applying relative transmittance reaches 23% and the alternating voltage that frequency is 30Hz drives liquid crystal cells, applies the DC voltage of 2V simultaneously, drives 60 minutes to it.Thereafter, make applying DC voltage value be 0V and only stop the applying of DC voltage, driving 30 minutes further in this condition.

About after image evaluation, the moment that self-stopping technology applies DC voltage rises to through 60 minutes, defines and be evaluated as " well " when relative transmittance returns to below 25%.When relative transmittance needs more than 30 minutes till returning to below 25%, define and be evaluated as " bad ".

Further, the after image evaluation based on said method is carried out under the temperature of liquid crystal cells is the temperature conditions of the state of 23 DEG C.Evaluation result is shown in table 3.

(evaluating based on the charge accumulation value exchanging the un-symmetrical change driven)

Then, applying frequency to this liquid crystal cells is the alternating voltage of 30Hz, while measure V-T curve (voltage-transmission rate curve), alternating voltage relative transmittance being reached 50% calculates as driving voltage.

Irradiate with LED light and carry out shading less than the mode of liquid crystal cells.And then, with the frequency of 1kHz, liquid crystal cells is applied to the 20mV square wave of 30 minutes.

Thereafter, while lighting LED, carry out the interchange driving that relative transmittance reaches 50%, measuring the V-F after firm lighting (voltage-scinti gram) curve, calculating the offset voltage value for eliminating the charge accumulation caused by the un-symmetrical change exchanging driving.Thereafter, within every 1 minute, measure smallest offset magnitude of voltage variable quantity, calculate maximum voltage value when changing to 30 minutes from after firm lighting.Now, when the variable quantity of peak excursion voltage is more than 20mV, defines and be evaluated as " bad ".In addition, when the variable quantity of peak excursion voltage is no more than 20mV, defines and be evaluated as " well ".

(based on the long-term after image evaluation driven)

Use this liquid crystal cells, under the isoperibol of 60 DEG C, apply the alternating voltage of the 8VPP of 100 hours with the frequency of 30Hz.Thereafter, make to present short-circuit condition between the pixel electrode of liquid crystal cells and counter electrode, directly at room temperature place one day.

After placement, be arranged on by liquid crystal cells between 2 polarization plates configuring in the mode that polarization axle is vertical, light backlight not executing under alive state, the arrangement angles of adjustment liquid crystal cells, reaches minimum to make the brightness of transmitted light.Then, will the rotation of the liquid crystal cells angle the darkest from the 2nd region of the 1st pixel be calculated as angle delta to the anglec of rotation during angle that the 1st region is the darkest.2nd region and the 1st region similarly, compare, calculate same angle delta by the 2nd pixel.Further, the mean value of the angle delta value of the 1st pixel and the 2nd pixel is calculated as the angle delta of liquid crystal cells.When the angle delta value of this liquid crystal cells is more than 0.2 degree, defines and be evaluated as " bad ".When the angle delta value of this liquid crystal cells is not more than 0.2 degree, defines and be evaluated as " well ".

[synthesis of polymkeric substance]

< synthesis example 1>

Add DA-414.03g (48.0mmol), METHYLPYRROLIDONE 141.3g to band stirring apparatus with being with in the 200ml tetra-neck flask of nitrogen ingress pipe, supplying nitrogen is while stir and make it dissolve.Stir this two amine aqueous solution while add CA-110.05g (46.0mmol) and METHYLPYRROLIDONE reaches 12 quality % to make solid component concentration, stir 20 hours under water temperature and obtain the solution (referred to as P1) of polyamic acid.Confirm the viscosity of this polyamic acid (P1) solution at 25 DEG C with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), result is 271mPas.

In this polyamic acid (P1) solution 27.82g, add METHYLPYRROLIDONE 11.72g and butyl cellosolve 13.18g, the concentration obtaining P1 is the aligning agent for liquid crystal of 6.0 quality %.

< synthesis example 2>

Add DA-43.04g (10.4mmol), DA-20.52g (3.1mmol), METHYLPYRROLIDONE 36.3g to band stirring apparatus with being with in the 50ml tetra-neck flask of nitrogen ingress pipe, supplying nitrogen is while stir and make it dissolve.Stir this two amine aqueous solution while add CA-12.64g (12.5mmol) and METHYLPYRROLIDONE reaches 12 quality % to make solid component concentration, stir 20 hours under water temperature and obtain the solution (referred to as P2) of polyamic acid.Confirm the viscosity of this polyamic acid (P2) solution at 25 DEG C with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), result is 316mPas.

In this polyamic acid (P2) solution 34.3g, add METHYLPYRROLIDONE 7.87g and butyl cellosolve 8.58g, the concentration obtaining P2 is the aligning agent for liquid crystal of 6.0 quality %.

< synthesis example 3>

Add DA-522.68g (79.2mmol), DA-610.52g (52.8mmol), METHYLPYRROLIDONE 310.1g to band stirring apparatus with being with in the 500ml tetra-neck flask of nitrogen ingress pipe, supplying nitrogen is while stir and make it dissolve.Stir this two amine aqueous solution while add CA-127.21g (124.7mmol) and METHYLPYRROLIDONE reaches 12 quality % to make solid component concentration, stir 20 hours under water temperature and obtain the solution (referred to as P3) of polyamic acid.Confirm the viscosity of this polyamic acid (P3) solution at 25 DEG C with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), result is 278mPas.

In this polyamic acid (P3) solution 271.4g, add METHYLPYRROLIDONE 132.3g and butyl cellosolve 134.5g, the concentration obtaining P3 is the aligning agent for liquid crystal of 6.0 quality %.

< synthesis example 4>

Add DA-118.5g (92.0mmol), METHYLPYRROLIDONE 211.4g to band stirring apparatus with being with in the 300ml tetra-neck flask of nitrogen ingress pipe, supplying nitrogen is while stir and make it dissolve.Stir this two amine aqueous solution while add CA-217.56g (89.5mmol) and METHYLPYRROLIDONE reaches 12 quality % to make solid component concentration, stir 20 hours under water temperature and obtain the solution (referred to as P4) of polyamic acid.Confirm the viscosity of this polyamic acid (P4) solution at 25 DEG C with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), result is 301mPas.

In this polyamic acid (P4) solution 25.2g, add METHYLPYRROLIDONE 9.86g, METHYLPYRROLIDONE solution 3.05g that APTES is 1.0 quality % and butyl cellosolve 12.71g, the concentration obtaining P4 is the aligning agent for liquid crystal of 6.0 quality %.

< synthesis example 5>

Add DA-26.15g (31.0mmol), METHYLPYRROLIDONE 70.65g to band stirring apparatus with being with in the 100ml tetra-neck flask of nitrogen ingress pipe, supplying nitrogen is while stir and make it dissolve.Stir this two amine aqueous solution while add CA-26.01g (30.5mmol) and METHYLPYRROLIDONE reaches 12 quality % to make solid component concentration, stir 20 hours under water temperature and obtain the solution (referred to as P5) of polyamic acid.Confirm the viscosity of this polyamic acid (P5) solution at 25 DEG C with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), result is 130mPas.

In this polyamic acid (P5) solution 18.05g, add METHYLPYRROLIDONE 7.05g, METHYLPYRROLIDONE solution 2.18g that APTES is 1.0 quality % and butyl cellosolve 9.09g, the concentration obtaining P5 is the aligning agent for liquid crystal of 6.0 quality %.

< synthesis example 6>

Add DA-24.02g (20.3mmol), DA-32.60g (8.7mmol), METHYLPYRROLIDONE 70.8g to band stirring apparatus with being with in the 100ml tetra-neck flask of nitrogen ingress pipe, supplying nitrogen is while stir and make it dissolve.Stir this two amine aqueous solution while add CA-25.61g (28.5mmol) and METHYLPYRROLIDONE reaches 12 quality % to make solid component concentration, stir 5 hours under water temperature, obtain the solution (referred to as P6) of polyamic acid.Confirm the viscosity of this polyamic acid (P6) solution at 25 DEG C with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), result is 249mPas.

In this polyamic acid (P6) solution 18.02g, add METHYLPYRROLIDONE 6.45g, METHYLPYRROLIDONE solution 2.13g that APTES is 1.0 quality % and butyl cellosolve 8.87g, the concentration obtaining P6 is the aligning agent for liquid crystal of 6.0 quality %.

< synthesis example 7>

Add DA-310.6g (35.4mmol), DA-73.55g (23.6mmol), METHYLPYRROLIDONE 136.2g to band stirring apparatus with being with in the 100ml tetra-neck flask of nitrogen ingress pipe, supplying nitrogen is while stir and make it dissolve.Stir this two amine aqueous solution while add CA-211.3g (57.6mmol) and METHYLPYRROLIDONE reaches 10 quality % to make solid component concentration, stir 5 hours under water temperature, obtain the solution (referred to as P7) of polyamic acid.Confirm the viscosity of this polyamic acid (P7) solution at 25 DEG C with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), result is 154mPas.

In this polyamic acid (P7) solution 58.97g, add METHYLPYRROLIDONE 38.69g, METHYLPYRROLIDONE solution 8.49g that APTES is 1.0 quality % and butyl cellosolve 35.38g, the concentration obtaining P7 is the aligning agent for liquid crystal of 6.0 quality %.

< synthesis example 8>

DA-43.80g (13.0mmol), DA-83.35g (13.0mmol) is added with being with in the 100ml tetra-neck flask of nitrogen ingress pipe to band stirring apparatus, add METHYLPYRROLIDONE 54.07g, supplying nitrogen is while stir and make it dissolve.While stirred under water-cooled by this two amine aqueous solution, add CA-12.84g (13.0mmol) and METHYLPYRROLIDONE 18.0g, stir 3 hours under water-cooled in a nitrogen atmosphere.Thereafter, add CA-22.29g (11.7mmol) and METHYLPYRROLIDONE 18.0g and stir and make it dissolve, stirring 3 hours under water-cooled, obtain the solution of polyamic acid (A8).Confirm the viscosity of this polyamic acid (A8) solution at 25 DEG C with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), result is 164mPas.

In this polyamic acid (P8) solution 20.77g, add METHYLPYRROLIDONE 20.77g and butyl cellosolve 10.06g, the concentration obtaining P8 is the aligning agent for liquid crystal of 6.0 quality %.

< synthesis example 9>

Add DA-44.38g (15.0mmol), DA-82.58g (10.0mmol), METHYLPYRROLIDONE 70.94g to band stirring apparatus with being with in the 100ml tetra-neck flask of nitrogen ingress pipe, supplying nitrogen is while stir and make it dissolve.Stir this two amine aqueous solution while add CA-15.13g (24.0mmol) and METHYLPYRROLIDONE reaches 12 quality % to make solid component concentration, stir 20 hours under water temperature and obtain the solution (referred to as P9) of polyamic acid.Confirm the viscosity of this polyamic acid (P9) solution at 25 DEG C with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), result is 202mPas.

In this polyamic acid (P9) solution 21.44g, add METHYLPYRROLIDONE 8.28g and butyl cellosolve 9.91g, the concentration obtaining P9 is the aligning agent for liquid crystal of 6.0 quality %.

< synthesis example 10>

Add DA-43.04g (10.0mmol), DA-84.03g (15.0mmol), METHYLPYRROLIDONE 72.74g to band stirring apparatus with being with in the 100ml tetra-neck flask of nitrogen ingress pipe, supplying nitrogen is while stir and make it dissolve.Stir this two amine aqueous solution while add CA-15.33g (24.0mmol) and METHYLPYRROLIDONE reaches 12 quality % to make solid component concentration, stir 20 hours under water temperature and obtain the solution (referred to as P10) of polyamic acid.Confirm the viscosity of this polyamic acid (P10) solution at 25 DEG C with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), result is 395mPas.

In this polyamic acid (P10) solution 20.42g, add METHYLPYRROLIDONE 8.10g and butyl cellosolve 9.46g, the concentration obtaining P10 is the aligning agent for liquid crystal of 6.0 quality %.

< synthesis example 11>

Add DA-41.55g (5.30mmol), DA-53.04g (10.6mmol), DA-62.11g (10.6mmol), METHYLPYRROLIDONE 71.33g to band stirring apparatus with being with in the 100ml tetra-neck flask of nitrogen ingress pipe, supplying nitrogen is while stir and make it dissolve.Stir this two amine aqueous solution while add CA-15.46g (25.0mmol) and METHYLPYRROLIDONE reaches 12 quality % to make solid component concentration, stir 20 hours under water temperature and obtain the solution (referred to as P11) of polyamic acid.Confirm the viscosity of this polyamic acid (P11) solution at 25 DEG C with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), result is 895mPas.

In this polyamic acid (P11) solution 20.57g, add METHYLPYRROLIDONE 10.15g and butyl cellosolve 9.57g, the concentration obtaining P11 is the aligning agent for liquid crystal of 4.6 quality %.

< synthesis example 13>

Adding DA-517.75g (62.0mmol) to band stirring apparatus with being with in the 200ml tetra-neck flask of nitrogen ingress pipe, adding METHYLPYRROLIDONE 139.1g, supplying nitrogen is while stir and make it dissolve.While this two amine aqueous solution is stirred under water-cooled, while add CA-112.91g (59.2mmol), and then interpolation METHYLPYRROLIDONE reaches 12 quality % to make solid component concentration, heat with 50 degree in a nitrogen atmosphere on one side, while stir, thus obtain the solution of polyamic acid (A1) 20 hours.Confirm the viscosity of this polyamic acid (P12) solution at 25 DEG C with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), result is 530mPas.

In this polyamic acid (P12) solution 50.00g, add METHYLPYRROLIDONE 43.95g, METHYLPYRROLIDONE solution 5.6g that APTES is 1.0 quality % and butyl cellosolve 24.89g, the concentration obtaining A1 is the aligning agent for liquid crystal of 4.5 quality %.

< synthesis example 12>

Adding DA-67.97g (40.0mmol) to band stirring apparatus with being with in the 200ml tetra-neck flask of nitrogen ingress pipe, adding METHYLPYRROLIDONE 98.6g, supplying nitrogen is while stir and make it dissolve.While stirred under water-cooled by this two amine aqueous solution, add CA-26.96g (35.5mmol) and METHYLPYRROLIDONE 35.9g, stir 3 hours under water-cooled in a nitrogen atmosphere.Thereafter, add DA-21.98g (10.0mmol) and METHYLPYRROLIDONE 17.9g and stir and make it dissolve.After DA-6 dissolves, add CA-33.00g (10.0mmol) and METHYLPYRROLIDONE 26.9g, again stir 3 hours under water-cooled in a nitrogen atmosphere, obtain the solution of polyamic acid (P13).Confirm the viscosity of this polyamic acid (P12) solution at 25 DEG C with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), result is 165mPas.

In this polyamic acid (P13) solution 50.00g, add METHYLPYRROLIDONE 10.55g, METHYLPYRROLIDONE solution 4.9g that APTES is 1.0 quality % and butyl cellosolve 16.37g, the concentration obtaining P13 is the solution of 6.0 quality %.

< embodiment 1>

The component that the polyamic acid solution obtained in synthesis example 1 (P1) and the polyamic acid solution (P4) obtained in synthesis example 4 reach 50:50 with mass ratio is mixed, thus obtains polyamic acid solution (A-1).

< embodiment 2>

The component that the polyamic acid solution obtained in synthesis example 1 (P1) and the polyamic acid solution (P5) obtained in synthesis example 5 reach 50:50 with mass ratio is mixed, thus obtains polyamic acid solution (A-2).

< embodiment 3>

The component that the polyamic acid solution obtained in synthesis example 2 (P2) and the polyamic acid solution (P6) obtained in synthesis example 6 reach 50:50 with mass ratio is mixed, thus obtains polyamic acid solution (A-3).

< embodiment 4>

The component that the polyamic acid solution obtained in synthesis example 3 (P3) and the polyamic acid solution (P6) obtained in synthesis example 6 reach 30:70 with mass ratio is mixed, thus obtains polyamic acid solution (A-4).

< embodiment 5>

The component that the polyamic acid solution obtained in synthesis example 11 (P11) and the polyamic acid solution (P7) obtained in synthesis example 7 reach 30:70 with mass ratio is mixed, thus obtains polyamic acid solution (A-5).

< embodiment 6>

The component that the polyamic acid solution obtained in synthesis example 9 (P9) and the polyamic acid solution (P6) obtained in synthesis example 6 reach 40:60 with mass ratio is mixed, thus obtains polyamic acid solution (A-6).

< embodiment 7>

The component that the polyamic acid solution obtained in synthesis example 9 (P9) and the polyamic acid solution (P7) obtained in synthesis example 7 reach 40:60 with mass ratio is mixed, thus obtains polyamic acid solution (A-7).

< comparative example 1>

Using the polyamic acid solution (P13) that obtains in synthesis example 13 as comparative example (B-1), and for evaluating.

< comparative example 2>

Using the polyamic acid solution (P4) that obtains in synthesis example 4 as comparative example (B-2), and for evaluating.

< comparative example 3>

Using the polyamic acid solution (P8) that obtains in synthesis example 8 as comparative example (B-3), and for evaluating.

< comparative example 4>

The polyamic acid solution obtained in synthesis example 13 (P13) is mixed than the component reaching 20:80 with mass weight with the polyamic acid solution (P12) obtained in synthesis example 12, thus obtains polyamic acid solution (B-4).

< comparative example 5>

The component that the polyamic acid solution obtained in synthesis example 10 (P10) and the polyamic acid solution (P6) obtained in synthesis example 6 reach 40:60 with mass ratio is mixed, thus obtains polyamic acid solution (B-5).

P1 ~ the P13 used in preparation for each polyamic acid solution of above-described embodiment 1 ~ 7 and comparative example 1 ~ 5, is shown in table 1 by tetracarboxylic dianhydride's composition, diamine component ratio.

In addition, the mixture ratio of each polyamic acid solution in embodiment 1 ~ 7 and comparative example 1 ~ 5 is shown in table 2.

And then, table 3 illustrate the film that uses embodiment 1 ~ 7 and the polyamic acid solution of comparative example 1 ~ 5 to make and visual perspective rate evaluations utilizing liquid crystal cells to obtain, after image evaluation, the after image evaluation driven based on long-term, based on the result of charge accumulation value evaluation of un-symmetrical change exchanging driving.

[table 1]

[table 2]

[table 3]

	Polymkeric substance	The die-out time of after image	Long-term driving is evaluated	Charge accumulation value is evaluated	Visual perspective rate
						Embodiment 1	A-1	Well	Well	Well	Well
Embodiment 2	A-2	Well	Well	Well	Well
						Embodiment 3	A-3	Well	Well	Well	Well
Embodiment 4	A-4	Well	Well	Well	Well
						Embodiment 5	A-5	Well	Well	Well	Well
Embodiment 6	A-6	Well	Well	Well	Well
						Embodiment 7	A-7	Well	Well	Well	Well
Comparative example 1	B-1	Well	Well	Bad	Well
						Comparative example 2	B-2	Well	Bad	Well	Well
Comparative example 3	B-3	Bad	Well	Bad	Well
						Comparative example 4	B-4	Well	Well	Bad	Bad

As above, the polyamic acid of the present invention made in embodiment 1 ~ 6 all shows good result in the evaluation of visual perspective rate, after image evaluation, the after image evaluation based on long-term driving, any one based on the charge accumulation value evaluation of the un-symmetrical change of interchange driving, but in comparative example 1 ~ 4 make polyamic acid above-mentioned assessment item any one in all can obtain bad result, especially in evaluating based on the charge accumulation value exchanging the un-symmetrical change driven, obviously different from the performance of polyamic acid of the present invention.

Claims

1. an aligning agent for liquid crystal, is characterized in that, it contains: comprise at least a kind of polyamic acid of cellular construction shown in following formula (I) and comprise at least a kind of polyamic acid of cellular construction shown in following formula (II),

R ¹represent the 4 valency organic groups be selected from following structure (III) and (IV) that can form fragrant family tetrabasic carboxylic acid,

R ⁵, R ⁶, R ⁷, R ⁸separately represent hydrogen atom or methyl,

R ³expression can form the divalent organic group with following structure (VI) or formula (VII) of diamines,

R ¹²represent the alkylidene of carbon number 2 ~ 8,

R ⁹, R ¹⁰separately be selected from hydrogen atom, methyl, ethyl, methoxyl, ethoxy, R ¹¹for ehter bond or methylene, a represents the integer of 1 ~ 4,

In formula (IX), R ¹³and R ¹⁴be the alkylidene of carbon number 1 ~ 3 independently of one another, Y ¹and Y ²be singly-bound ,-O-,-S-or ester bond independently of one another, Z is oxygen atom or sulphur atom.

2. aligning agent for liquid crystal according to claim 1, wherein, the polyamic acid composition comprising cellular construction shown in described formula (I) is 2:8 ~ 7:3 with the polyamic acid composition comprising cellular construction shown in described formula (II) containing ratio by quality ratio.

3. aligning agent for liquid crystal according to claim 1 and 2, wherein, the R in described formula (I) ³it is the divalent organic group that can form two (4-amino-benzene oxygen) benzene of 1,3-or two (4-amino-benzene oxygen) pentane of 1,5-.

4. the aligning agent for liquid crystal according to any one of claims 1 to 3, wherein, the R in described formula (II) ⁴it is the organic group forming diaminodiphenyl ether or diaminodiphenyl-methane or two (4-aminophenethyl) urea.

5. the aligning agent for liquid crystal according to any one of Claims 1 to 4, wherein, the R in described formula (I) ¹the organic group that can form pyromellitic acid, the R in described formula (II) ²for the organic group of cyclo-butane tetrabasic carboxylic acid can be formed.

6. a liquid crystal orientation film, it is coated on by the aligning agent for liquid crystal according to any one of Claims 1 to 5 on substrate and after burning till, carries out brushing process and formed.

7. liquid crystal represents an element, it uses liquid crystal orientation film, and described liquid crystal orientation film is coated on by the aligning agent for liquid crystal according to any one of Claims 1 to 5 on substrate and after burning till, carries out brushing process and formed.